TWI504504B - Attached copper foil - Google Patents

Description

Carrier copper foil

The present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board.

The printed wiring board is usually produced by a step of forming a conductor pattern by etching a copper foil surface after the copper foil and the insulating substrate are bonded to each other to form a copper clad laminate. With the increase in the demand for miniaturization and high performance of electronic devices, the high-density mounting of components and the high-frequency development of signals, and the miniaturization of conductor patterns (fine pitch) are required for printed wiring boards. Or) to deal with high frequencies and so on.

In order to reduce the pitch, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less has recently been required. However, such an extremely thin copper foil is likely to be damaged or wrinkled when manufacturing a printed wiring board due to low mechanical strength, and thus has been utilized. A carrier-attached copper foil having a metal foil having a thickness as a carrier and an extremely thin copper layer plated thereon via a peeling layer. After bonding the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, the carrier is peeled off by the peeling layer. A method of etching an extremely thin copper layer by a sulfuric acid-hydrogen peroxide-based etchant by using a resist to form a circuit pattern on an exposed ultra-thin copper layer (MSAP: Modified-Semi-Additive-Process) A process is formed to form a fine circuit.

Here, the surface of the ultra-thin copper layer which is the carrier-attached copper foil which is the contact surface of the resin is required to have sufficient peeling strength of the extremely thin copper layer and the resin substrate, and is heated at a high temperature and wet. After the treatment, welding, chemical treatment, etc., the peel strength can be sufficiently maintained. As a method of increasing the peel strength between the ultra-thin copper layer and the resin substrate, a method of attaching a large amount of roughened particles to an extremely thin copper layer having an increased surface profile (concavity and roughness) is generally representative.

However, in a printed wiring board, in particular, a semiconductor package substrate in which a fine circuit pattern must be formed uses such an extremely thin copper layer having a large profile (concavity, roughness, roughness), and unnecessary copper particles remain during circuit etching. , causing problems such as poor insulation between circuit patterns.

Therefore, in WO2004/005588 (Patent Document 1), it is attempted to use a copper foil with a carrier which does not roughen the surface of the ultra-thin copper layer as a carrier-attached copper foil for microcircuit applications typified by a semiconductor package substrate. The adhesion (peeling strength) of the ultra-thin copper layer and the resin which are not subjected to the roughening treatment is affected by the low profile (concavity, roughness, roughness) and the conventional copper foil for printed wiring boards. Reduce the tendency. Therefore, further improvement is required for the copper foil with a carrier.

In JP-A-2007-007937 (Patent Document 2) and Japanese Patent Laid-Open Publication No. 2010-006071 (Patent Document 3), it is described in the case of a very thin copper foil with a polyimine. a Ni layer or/and a Ni alloy layer, a chromate layer, a Cr layer or/and a Cr alloy layer, a Ni layer and a chromate layer, and a Ni layer and a Cr layer are provided on the surface of the resin substrate that is in contact with (and subsequently). . By providing such a surface treatment layer, the adhesion strength between the polyimide film and the ultra-thin copper foil with a carrier can be obtained without the need for roughening treatment or reduction in the degree of roughening (fineness). Then the intensity. Further, surface treatment with a decane coupling agent or rust-preventing treatment is also described.

[Patent Document 1] WO2004/005588

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-007937

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-006071

Up to now, in the development of the carrier-attached copper foil, the center of gravity has been placed to ensure the peel strength of the ultra-thin copper layer and the resin substrate. Therefore, regarding fine pitching, sufficient research has not been conducted, and there is still room for improvement. Accordingly, it is an object of the present invention to provide a copper foil with a carrier suitable for forming a fine pitch. Specifically, it is an object of the invention to provide a copper foil with a carrier which can form a wiring which is finer than L/S=20 μm/20 μm which is considered to be the limit of MSAP formation so far.

In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that the surface of the ultra-thin copper layer is reduced in thickness and the finely roughened copper layer is uniformly formed in the plane in the ultra-thin copper layer. A uniform and low-thickness roughening treatment surface is formed. Further, it has been found that the copper foil with a carrier is extremely effective for forming a fine pitch.

The present invention is based on the above findings, and in one aspect is a copper foil with a carrier which is provided with a carrier, a release layer, an extremely thin copper layer, and an arbitrary resin layer, and has a very thin copper layer surface. The average value of Rz is 1.5 μm or less, and the standard deviation of Rz is 0.1 μm or less, measured by a contact-type roughness meter in accordance with JIS B0601-1982.

In another aspect, the invention provides a copper foil with a carrier, which is provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Rt of the surface of the ultra-thin copper layer is utilized. The contact type roughness meter was measured in accordance with JIS B0601-2001 to be 2.0 μm or less, and the standard deviation of Rt was 0.1 μm or less.

In still another aspect of the present invention, a copper foil with a carrier is provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and an average value of Ra of the surface of the ultra-thin copper layer is The contact roughness meter was measured in accordance with JIS B0601-1982 and was 0.2 μm or less, and the standard deviation of Ra was 0.03 μm or less.

In one embodiment of the copper foil with carrier of the present invention, the ultra-thin copper layer is roughened.

In still another aspect, the present invention is a printed wiring board produced by using the copper foil with a carrier of the present invention.

In still another aspect of the invention, a printed circuit board is produced using the copper foil with a carrier of the present invention.

In still another aspect of the invention, a copper clad laminate is produced using the copper foil with a carrier of the present invention.

The copper foil with carrier of the present invention is suitable for forming a fine pitch, for example, a wiring which is considered to be a finer L/S=20 μm/20 μm which is a limit which can be formed by the MSAP step, for example, a fineness of L/S = 15 μm / 15 μm. Wiring. In particular, in the present invention, the in-plane uniformity of the surface roughness of the ultra-thin copper layer is high, whereby the in-plane uniformity is improved in the flashing when the circuit is formed by the MSAP method, so that the yield can be expected to be improved. .

Fig. 1 is a schematic view showing the manner in which the foil is transported using a drum.

Fig. 2 is a schematic view showing a foil transfer method using zigzag folding.

Fig. 3 is a view showing the steps A to C of a specific example of a method of producing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 4 is a view showing steps D to F of a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 5 is a view showing steps G to I of a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Figure 6 is a view showing the concrete manufacturing method of the printed wiring board using the copper foil with a carrier of the present invention; Steps J to K of the example.

<1. Carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin. A film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like) is provided.

As the carrier which can be used in the present invention, copper foil is preferably used. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath on a drum of titanium or stainless steel, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, or Mg is added, or Ni and Si may be added. A copper alloy such as a copper alloy. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a suitable thickness as a function of the carrier, and may be, for example, 12 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 70 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

<2. Peeling layer>

A release layer is provided on the carrier. Other layers may also be provided between the copper foil carrier and the release layer. As the release layer, the carrier copper foil can be provided with any release layer known to the manufacturer. For example, the release layer preferably comprises Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or alloys thereof, or such hydrates, or oxides thereof, or Any one or more layers of the organic substance are formed. The release layer can also be composed of a plurality of layers. Furthermore, the release layer can have an anti-diffusion function. Here, the so-called non-diffusion The function is to prevent the element from the base material from diffusing to the side of the extremely thin copper layer.

In one embodiment of the present invention, the release layer is formed from the carrier side by any one of elements of the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al. a single metal layer or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al (these have anti-diffusion functions) And a layer composed of a hydrate or an oxide or an organic substance of one or more elements selected from the group consisting of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al.

Further, for example, the release layer may be composed of a single metal layer composed of any one of elemental groups of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. Or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, and secondly, Cr, Ni, Co, Fe a single metal layer composed of any one of elemental groups of Mo, Ti, W, P, Cu, Al, Zn, or selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu An alloy layer composed of one or more elements of the element group of Al or Zn. Further, the total adhesion amount of each element can be, for example, 1 to 6000 μg/dm ² . Further, a layer structure which can be used as a release layer can also be used for other layers.

The release layer is preferably composed of two layers of Ni and Cr. In this case, the Ni layer is laminated in such a manner as to be in contact with the interface with the copper foil carrier, and the Cr layer is laminated in such a manner as to contact the interface with the extremely thin copper layer.

The release layer can be obtained, for example, by wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, or PDV. From the viewpoint of cost, electroplating is preferred.

Further, for example, the release layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy and chromium on a carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, the nickel of the peeling layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin copper layer. Ni deposition amount of the release layer is preferably 100μg / dm ² or more and 40000μg / dm ² or less, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² Hereinafter, it is more preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium adhesion in the release layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the peeling layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the surface opposite to the carrier.

Furthermore, the release layer can also be disposed on both sides of the carrier.

<3. Very thin copper layer>

An extremely thin copper layer is provided on the peeling layer. Other layers may also be provided between the release layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath having copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and can form a copper foil at a high current density using a conventional electrolytic copper foil. In terms of aspect, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 2 to 5 μm. Furthermore, an extremely thin copper layer may be provided on both sides of the carrier. Further, a layer structure which can be used as a release layer can also be used for other layers.

<4. Roughening treatment>

The surface of the ultra-thin copper layer may be provided with a roughened layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be formed, for example, by forming roughened particles using copper or a copper alloy. From the viewpoint of forming a fine pitch, the roughened layer is preferably composed of fine particles. Regarding the plating conditions in the case of forming the roughened particles, if the current density is increased, the copper concentration in the plating solution is lowered, or the coulomb amount is increased, the particles tend to be fine.

The roughening treatment layer may be composed of the following electroplated particles: a monomer selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc or an alloy containing any one or more. Composition.

In order to improve the in-plane uniformity of the surface roughness of the surface-treated surface, it is effective to stably maintain the anode-cathode distance when the roughened layer is formed. Unlimited, industrial students From the viewpoint of production, it is effective to secure a fixed interelectrode distance by using a tumbler or the like as a supporting medium. Fig. 1 is a schematic view showing the manner of transporting the foil. The carrier copper foil conveyed by the conveyance roller is supported by a rotating drum, and a roughened particle layer is formed by electrolytic plating on the surface of the ultra-thin copper layer. The treated surface of the carrier copper foil supported by the drum has both a cathode, and each electrolytic plating is performed in the plating liquid between the drum and the anode provided in a manner opposed to the drum. On the other hand, FIG. 2 is a schematic view showing a foil transfer method using a conventional bending. This method has a problem that it is difficult to fix the distance between the anode and the cathode due to the influence of the electrolyte solution and the tension of the foil. Furthermore, in order to maintain the distance between the anode and the cathode at the time of forming the roughened layer by the use of the foil-transfer method, it is better to increase the tension for transporting the foil and shorten the distance between the transport rollers. effective.

As shown in Fig. 1, the foil transfer method can be used not only for the roughening treatment but also for the formation of the peeling layer and the formation of an extremely thin copper layer. The reason for this is that the thickness accuracy of the peeling layer or the ultra-thin copper layer can be improved by using a foil transfer method. Furthermore, in order to fix the anode-cathode distance when the peeling layer or the ultra-thin copper layer is formed by the use of the bending foil transfer method, the tension for transporting the foil is increased, and the transfer roller is shortened as compared with the conventional one. The distance is more effective.

The distance between the electrodes is not limited. If the distance is too long, the production cost is increased. On the other hand, if the surface unevenness is too large, the in-plane unevenness tends to be large. Therefore, it is usually preferably 3 to 100 mm, more preferably 5 to 80 mm.

Further, after the roughening treatment, secondary particles or tertiary particles and/or a rust-preventing layer may be formed from a monomer, an alloy or the like of nickel, cobalt, copper or zinc, and the surface may be subjected to chromate treatment or decane coupling. Processing and other processing. That is, one or more layers selected from the group consisting of a rust preventive layer, a chromate treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be not coarsened on the surface of the extremely thin copper layer. One or more layers selected from the group consisting of a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer are formed by a treatment. Moreover, these surface treatments have almost no effect on the surface roughness of the ultra-thin copper layer.

Very thin copper layer surface (when performing various surface treatments such as roughening treatment) The surface of the ultra-thin copper layer after surface treatment (also referred to as "surface-treated surface") is averaged by Rz (ten-point average roughness) when measured by a contact-type roughness meter according to JIS B0601-1982. The value is set to 1.5 μm or less, which is extremely advantageous from the viewpoint of forming a fine pitch. The average value of Rz is preferably 1.4 μm or less, more preferably 1.3 μm or less, still more preferably 1.2 μm or less, still more preferably 1.0 μm or less, still more preferably 0.8 μm or less. However, when the average value of Rz is too small, the adhesion to the resin is lowered. In this respect, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, and most preferably 0.5 μm or more. . In the present invention, the average value of Rz is an average value of each Rz obtained when the standard deviation of Rz is obtained by the method described below.

In the present invention, the standard deviation of Rz on the surface of the ultra-thin copper layer can be 0.1 μm or less, preferably 0.05 μm or less, and for example, 0.01 to 0.7 μm. The standard deviation of Rz on the surface of the extremely thin copper layer was determined from the in-plane measurement data of 100 points. In addition, the measurement data of 100 points in the plane was obtained by dividing the 550 mm square sheet into 10 sections in the longitudinal direction and the lateral direction, and measuring the central portions of the 100 partially divided regions. This method uses this method in order to maintain in-plane uniformity, but the verification method is not limited to this. For example, even if a sample of a size of 550 mm × 440 mm to 400 mm × 200 mm which is generally used is divided into 100 parts in the plane (divided into 10 parts in the vertical and horizontal directions), the same information can be taken.

Further, from the viewpoint of the formation of the fine pitch, the surface of the ultra-thin copper layer is preferably such that the average value of Rt (maximum cross-sectional height) is 2.0 μm or less when measured by a contact-type roughness meter in accordance with JIS B0601-2001. It is preferably 1.8 μm or less, preferably 1.5 μm or less, preferably 1.3 μm or less, or preferably 1.1 μm or less. However, when the average value of Rt is too small, the adhesion to the resin is lowered. In this respect, it is preferably 0.5 μm or more, more preferably 0.6 μm or more, and still more preferably 0.8 μm or more. In the present invention, the average value of Rt is an average value of each Rt obtained when the standard deviation of Rt is obtained by the method described below.

In the present invention, further, the standard deviation of the Rt of the surface of the ultra-thin copper layer can be set. It is 0.1 μm or less, preferably 0.05 μm or less, and for example, 0.01 to 0.6 μm. The Rt standard deviation of the surface of the ultra-thin copper layer was obtained by measuring the data at 100 points in the same manner as Rz.

In the case of the formation of the fine pitch, the surface of the ultra-thin copper layer is preferably 0.2 μm or less when the average value of Ra (arithmetic mean roughness) is measured by a contact-type roughness meter in accordance with JIS B0601-1982. More preferably, it is 0.18 μm or less, and preferably 0.15 μm or less. However, when the average value of Ra is too small, the adhesion to the resin is lowered. In this respect, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.12 μm or more, and most preferably 0.13 μm or more. . In the present invention, the average value of Ra is an average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

Further, in the present invention, the Ra standard deviation of the surface of the ultra-thin copper layer can be made 0.03 μm or less, preferably 0.02 μm or less, and for example, 0.001 to 0.03 μm. The standard deviation of Ra on the surface of the ultra-thin copper layer was determined in the same manner as Rz based on the measurement data of 100 points in the plane.

In the case where an insulating substrate such as a resin or a resin layer is attached to a copper foil, a printed wiring board, or a copper clad laminated board with a resin layer attached to the surface of the ultra-thin copper layer, the insulating substrate is melted and removed. Thereby, the surface roughness (Ra, Rt, Rz) can be measured on the surface of the copper circuit or the copper foil.

<5. Other surface treatment>

After the roughening treatment, a heat-resistant layer or a rust-preventing layer may be formed using a monomer, an alloy, or the like of nickel, cobalt, copper, or zinc, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventive layer may be formed by using a monomer, an alloy such as nickel, cobalt, copper or zinc, or the like, without further performing a roughening treatment, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be formed in an extremely thin copper layer. Surface formation selected from One or more layers of the group consisting of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer. Further, the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may each be formed of, for example, two or more layers and three or more layers.

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements in the group of bismuth, or may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and lanthanum. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements in the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50% by weight to 99% by weight of nickel, and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The total amount of zinc and nickel attached to the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the nickel adhesion amount to the zinc adhesion amount (=the adhesion amount of nickel/the adhesion amount of zinc) of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 1.5 to 10. Further, the nickel adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is difficult when the inner wall portion of the through hole or the via hole is brought into contact with the degreasing liquid. The binder solution is corroded, and the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer having a deposition amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and the adhesion amount is The tin alloy layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² , may be any of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. A composition. Further, the heat-resistant layer and/or the rust-preventive layer preferably have a total adhesion amount of nickel or a nickel alloy to tin of 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the copper foil with a carrier is processed into a printed wiring board, and the peeling strength of the circuit, the chemical-resistant deterioration rate of the peeling strength, and the like are improved.

Further, as the decane coupling agent used for the decane coupling treatment, a known decane coupling agent may be used, and for example, an amine decane coupling agent, an epoxy decane coupling agent or a decyl decane coupling agent may be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene oxy propyl trimethoxy decane, γ-glycidoxy propyl trimethoxy decane may also be used. , 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-3 -(4-(3-Aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer can be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amino decane coupling agent herein may be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-amine Ethylethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyl Trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-amine Propyl triethoxy decane, 4-aminobutyl triethoxy decane, (aminoethylaminomethyl) phenethyl trimethoxy decane, N-(2-aminoethyl-3 -aminopropyl)trimethoxydecane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl) Trimethoxydecane, aminophenyltrimethoxydecane, 3-(1- Aminopropyloxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyltris(methoxyethoxyethoxy)decane, 3-aminopropyl Triethoxy decane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxy Base decane, bis(2-hydroxyethyl)-3-aminopropyltriethoxy decane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, (N,N- Dimethyl-3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N-styryl Methyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxy A group consisting of decane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane.

The decane coupling treatment layer is preferably set to 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/m in terms of ruthenium atom. ² range. In the case of the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Further, the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the decane coupling treatment layer or the chromate-treated layer may be internationally numbered WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japan Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, or Japanese Special Open 2013- Surface treatment as described in No. 19056.

[Resin layer on very thin copper layer]

The extremely thin copper layer of the copper foil with a carrier of the present invention (in the case of surface treatment of a very thin copper layer, the surface treatment layer formed on the extremely thin copper layer by the surface treatment) is provided with a resin. Floor. The above resin layer may also be an insulating resin layer.

The resin layer may be a resin, that is, an adhesive, or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes the following State: Even if the surface is touched with a finger, there is no adhesive feeling, and the insulating resin layer can be stored in an overlapping manner, and if it is further subjected to heat treatment, a hardening reaction is caused.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, a resin (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) can be used. And/or a method of forming a resin layer, and forming a device: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. 11-5828, Japanese Patent Laid-Open No. 11- No. 140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444 No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application No. 2004-349654 No., Japanese Patent No. 4,286,060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, Japanese Patent Publication No. WO2004/005588, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Publication No. 2013-19056.

In addition, the type of the resin layer is not particularly limited, and examples thereof include one or more resins selected from the group consisting of epoxy resins, polyimine resins, and polyfunctional cyanates. Compound, maleimide compound, polymaleimide compound, maleic imine resin, aromatic maleimide resin, polyvinyl acetaldehyde resin, urethane resin, polyether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, Polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide III Resin, thermosetting polyphenylene ether resin, cyanate ester resin, acid anhydride, acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2- Bis(4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, Alkoxysilane modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, Phenoxy group, polymer epoxy resin, aromatic polyamine, fluororesin, bisphenol, block copolymer polyimine resin and cyanoester resin.

Further, the epoxy resin has two or more epoxy groups in its molecule, and can be used without any problem as long as it can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in the molecule. Further, one or two or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol may be used. AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac type epoxy resin, naphthalene ring Oxygen resin, brominated bisphenol A epoxy resin, o-cresol novolak epoxy resin, rubber modified bisphenol A epoxy resin, glycidylamine epoxy resin, triglycidyl isocyanurate, Glycidylamine compound such as N,N-diglycidylaniline or dihydrophthalic acid condensed water Glycidyl ester compound such as glyceride, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin Alternatively, a hydrogenated body or a halogenated body of the above epoxy resin may be used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin is preferably, for example, a molecule having two or more epoxy groups in the molecule, from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9, Epoxy resin obtained in the form of a derivative of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).

The epoxy resin obtained in the form of a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10 - a compound represented by the following formula 1 (HCA-NQ) or 2 (HCA-HQ), which is reacted with naphthoquinone or hydroquinone to form a compound represented by the following OH group; The epoxy resin reacts to form a phosphorus-containing epoxy resin.

[Chemical 2]

The phosphorus-containing epoxy resin which is the above-mentioned E component which is obtained as a raw material is preferably a compound in which one or two types of structural formulas represented by any one of the following formulas 3 to 5 are used in combination. The reason for this is that the stability of the resin quality in the semi-hardened state is excellent, and the flame retardancy effect is high.

[Chemical 4]

Further, as the brominated epoxy resin, a known bromination can be used. (brominated) epoxy resin. For example, it is preferable that the brominated epoxy resin is used in combination with one or two kinds of epoxy groups having two or more epoxy groups, and is represented by a compound 6 obtained from a derivative of tetrabromobisphenol A. A brominated epoxy resin having a structural formula and a brominated epoxy resin having a structural formula represented by the following formula 7.

As the maleic imine resin or the aromatic maleimide resin, the maleimide compound or the polymaleimide compound, a known maleic imine resin or aromatic mala can be used. A quinone imine resin or a maleic imine compound or a polymaleimide compound. For example, as a maleic imine resin or an aromatic maleic imine resin or a maleimide compound or a polymaleimide compound, 4,4'-diphenylmethane bismale can be used. Yttrium, polyphenylmethane maleimide, meta-phenyl bis-maleimide, bisphenol A diphenyl ether, bismaleimide, 3,3'-dimethyl-5,5 '-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether double Maleidin, 4,4'-diphenylindole, bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-double (4-horse An imine phenoxy)benzene, a polymer obtained by polymerizing the above compound with the above compound or other compound, and the like. Further, the maleic imine resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may have two or more maleimine groups in the molecule. A polymeric adduct formed by polymerizing an aromatic maleic imine resin with a polyamine or an aromatic polyamine.

As the polyamine or aromatic polyamine, a known polyamine or an aromatic polyamine can be used. For example, as the polyamine or aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2, can be used. 6-Diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4 '-Diamino-3-methyldiphenyl ether, 4,4'-two Aminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylanthracene, bis(4-aminophenyl)phenylamine, isophthalate Amine, p-xylylenediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl -4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2',5,5'-tetrachloro-4, 4'-Diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane , 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl-4-aminophenyl)phenylethane, ethylenediamine and Diamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and a polymer obtained by polymerizing the above compound with the above compound or other compound. Further, one or two or more kinds of known polyamines and/or aromatic polyamines or the above polyamines or aromatic polyamines may be used.

As the phenoxy resin, a known phenoxy resin can be used. Further, as the phenoxy resin, those synthesized by the reaction of bisphenol and a divalent epoxy resin can be used. As the epoxy resin, a known epoxy resin and/or the above epoxy resin can be used.

As the bisphenol, a known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9, 10) can be used. -Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide) Bisphenol obtained in the form of an adduct of an anthracene such as hydroquinone or naphthoquinone.

As the linear polymer having a crosslinkable functional group, a linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group such as a hydroxyl group or a carboxyl group which contributes to the hardening reaction of the epoxy resin. Further, the linear polymer having a crosslinkable functional group is preferably an organic solvent which is soluble in a boiling point of 50 ° C to 200 ° C. When the linear polymer having a functional group is specifically exemplified herein, it is a polyvinyl acetaldehyde resin, a phenoxy resin, a polyether oxime resin, a polyamidoximine resin, or the like.

The above resin layer may contain a crosslinking agent. As the crosslinking agent, a known crosslinking agent can be used. For example, a urethane-based resin can be used as the crosslinking agent.

A well-known rubber resin can be used for the said rubber-type resin. For example, the above rubber resin system It is described as a concept including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, and acrylic resin. Rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, and the like. Further, in order to secure the heat resistance of the formed resin layer, it is also useful to use a heat-resistant synthetic rubber such as a nitrile rubber, a chloroprene rubber, a ruthenium rubber or a urethane rubber. In order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamidoximine resin, it is preferable to provide various functional groups at both ends. In particular, the use of CTBN (carboxy terminal butadiene nitrile) is useful. Further, when the acrylonitrile butadiene rubber is also a carboxyl group-modified body, an epoxy resin and a crosslinked structure can be obtained, and the flexibility of the resin layer after curing can be improved. As the carboxyl modified body, a carboxyl terminal nitrile rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), or a carboxyl modified nitrile rubber (C-NBR) can be used.

As the above polyamidoximine resin, a known polyamidimide resin can be used. Further, as the polyimine amide resin, for example, a solvent such as N-methyl-2-pyrrolidone or/N,N-dimethylacetamide or the like may be used. A benzophenone tetracarboxylic anhydride and a resin obtained by heating a bitolylene diisocyanate, or by N-methyl-2-pyrrolidone or/and N,N-dimethylacetamide It is obtained by heating benzene trimellitic anhydride, diphenylmethane diisocyanate, and carboxyl terminal acrylonitrile-butadiene rubber in a solvent.

As the rubber-modified polyamidoximine resin, a known rubber-modified polyamidoximine resin can be used. The rubber-modified polyamidoximine resin is obtained by reacting a polyamide amine imide resin with a rubber resin. The use of the polyamidoximine resin in a reaction with a rubber resin is carried out in order to improve the flexibility of the polyamide amidine resin itself. In other words, the polyamidoximine resin is reacted with a rubber resin, and one of the acid components (such as cyclohexanedicarboxylic acid) of the polyamidoximine resin is partially substituted with a rubber component. As the polyamidoximine resin, a known polyamidoximine resin can be used. Further, as the rubber resin, a known rubber resin or the above rubber resin can be used. For the polymerization of rubber modified polyamidoquinone imide resin, used to dissolve polyamidoximine resin and rubberiness The solvent of the resin is preferably one or more kinds of dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylammonium, nitromethane, and nitrate. Ethylethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like.

As the phosphazene-based resin, a known phosphazene-based resin can be used. The phosphazene-based resin contains a resin having a double bond phosphazene containing phosphorus and nitrogen as constituent elements. The phosphazene-based resin can dramatically improve the flame retardancy by the synergistic effect of nitrogen and phosphorus in the molecule. Further, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, an effect of stably present in the resin to prevent migration can be obtained.

As the fluororesin, a known fluororesin can be used. Further, as the fluororesin, for example, PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and FEP (tetrafluoroethylene-hexafluoropropylene) can be used. Copolymer (tetrafluorohexafluoride), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluorinated)), PCTFE (polychlorotrifluoroethylene (trifluoride)), A fluororesin composed of at least one of a polyarylene, an aromatic polysulfide, and an aromatic polyether, and a fluororesin.

Further, the resin layer may contain a resin curing agent. As the resin curing agent, a known resin curing agent can be used. For example, as the resin curing agent, an amine such as dicyanodiamine, an imidazole or an aromatic amine, a phenol such as bisphenol A or brominated bisphenol A, a phenol novolak resin, and a cresol novolak resin can be used. An anhydride such as a novolac type or a phthalic anhydride, a biphenyl type phenol type resin, or a phenol aralkyl type phenol type resin. Further, the resin layer may contain one or more kinds of the above-mentioned resin curing agents. These hardeners are especially effective for epoxy resins.

Specific examples of the above biphenyl type phenol-based resin are shown in Chemical Formula 8.

[化8]

Further, a specific example of the above phenol aralkyl type phenol resin is shown in Chemical Formula 9.

As the imidazole, a known one can be used, and examples thereof include 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methylimidazole. , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-benzene Methyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. may be used singly or in combination.

Further, among them, an imidazole having a structural formula represented by the following formula 10 is preferably used. By using the imidazole of the structural formula represented by the chemical formula 10, the moisture absorption resistance of the resin layer in a semi-hardened state can be remarkably improved, and the long-term storage stability is excellent. The reason for this is that the imidazole is used as a catalytic action in the curing of the epoxy resin, and functions as a reaction initiator for causing the self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

As the resin curing agent for the above amines, a known amine can be used. Further, as the resin curing agent for the amine, for example, the above polyamine or aromatic polyamine may be used, or an aromatic polyamine or a polyamine may be used, and the epoxy resin or the polycarboxylic acid may be used. One or two or more of the group of amine adducts obtained by acid polymerization or condensation. Further, as the resin hardener of the above amine, 4,4'-diaminodiphenylene fluorene, 3,3'-diaminodiphenylene fluorene, 4,4-diamino group is preferably used. Any one or more of biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(4-aminophenoxy)phenyl]anthracene.

The above resin layer may contain a hardening accelerator. As the hardening accelerator, a known hardening accelerator can be used. For example, as the hardening accelerator, a tertiary amine, an imidazole, a urea-based hardening accelerator, or the like can be used.

The above resin layer may contain a reaction catalyst. As the reaction catalyst, a known reaction catalyst can be used. For example, finely pulverized ceria, antimony trioxide or the like can be used as a reaction catalyst.

The acid anhydride of the above polycarboxylic acid is preferably a component which functions as a hardener of an epoxy resin. Further, the acid anhydride of the above polyvalent carboxylic acid is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyl Phthalic anhydride, nadic acid, methyl acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.

The above polyvinyl acetal resin may have a functional group other than a hydroxyl group and a hydroxyl group which can be polymerized with an epoxy resin or a maleimide compound. Further, the polyvinyl acetal resin may be one in which a carboxyl group, an amine group or an unsaturated double bond is introduced into the molecule.

The aromatic polyamine resin polymer is obtained by reacting an aromatic polyamide resin with a rubber resin. Here, the aromatic polyamine resin refers to a compound which is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. At this time, the aromatic diamine is 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl hydrazine, m-xylylenediamine, 3,3'-diaminodi Phenyl ether and the like. Further, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.

As the rubbery resin which can be reacted with the above aromatic polyamine resin, a known rubber resin or the above rubber resin can be used.

In order to etch the copper foil after processing the copper-clad laminate, the aromatic polyimide resin polymer is not damaged by the undercut due to the etching solution.

Further, the resin layer may be formed with a hardened resin layer from the side of the copper foil (that is, on the side of the extremely thin copper layer with the carrier copper foil) (the so-called "hardened resin layer" means a resin layer which is hardened), and semi-hardening. A resin layer of a resin layer. The hardened resin layer may be composed of any of a resin component having a thermal expansion coefficient of 0 ppm/° C. to 25 ppm/° C., a polyamidimide resin, and a composite resin.

Further, a semi-hardened resin layer having a thermal expansion coefficient after curing of from 0 ppm/° C. to 50 ppm/° C. may be provided on the cured resin layer. Further, the thermal expansion coefficient of the entire resin layer obtained by curing the cured resin layer and the semi-cured resin layer may be 40 ppm/° C. or less. The glass transition temperature of the above-mentioned cured resin layer may be 300 ° C or more. Further, the semi-cured resin layer may be formed by using a maleic imine resin or an aromatic maleimide resin. Used to form the above semi-hardening The resin composition of the resin layer is preferably a linear polymer comprising a maleic imide resin, an epoxy resin, and a functional group having crosslinkable. As the epoxy resin, a known epoxy resin or an epoxy resin described in the present specification can be used. Further, as the linear polymer of the maleic imine resin, the aromatic maleic imine resin, and the functional group capable of crosslinking, a known maleic imine resin or aromatic mala can be used. An imide resin, a linear polymer having a crosslinkable functional group, or a maleic imine resin, an aromatic maleimide resin, or a linear polymer having a crosslinkable functional group.

Further, in the case of providing a copper foil with a carrier layer having a resin layer suitable for the production of a three-dimensionally formed printed wiring board, the cured resin layer is preferably a cured polymer layer having flexibility. The polymer polymer layer is preferably composed of a resin having a glass transition temperature of 150 ° C or higher in order to be able to withstand the solder mounting step. The polymer layer is preferably composed of a polyamide resin, a polyether oxime resin, an aromatic polyamide resin, a phenoxy resin, a polyimide resin, a polyvinyl acetaldehyde resin, or a polyamidimide. Any one or two or more kinds of mixed resins of the resin. Further, the thickness of the polymer layer is preferably from 3 μm to 10 μm.

In addition, the polymer layer may be one or more selected from the group consisting of an epoxy resin, a maleimide resin, a phenol resin, and a urethane resin. Further, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the epoxy resin composition contains each component of the following A component to E component.

Component A: one of a group of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins selected from the group consisting of liquid bisphenol A type epoxy resins selected from room temperature. Or two or more types of epoxy resins.

Component B: High heat resistant epoxy resin.

Component C: a phosphorus-containing flame retardant resin which is one of a phosphorus-containing epoxy resin and a phosphazene-based resin or a resin obtained by mixing the same.

Component D: a liquid having a property soluble in a solvent having a boiling point of 50 ° C to 200 ° C A rubber-modified polyamidoximine resin modified from a rubber component.

Component E: Resin hardener.

The component B is a "high heat-resistant epoxy resin" in which the glass transition point Tg is high. Here, the "high heat resistant epoxy resin" is preferably a polyfunctional epoxy resin such as a novolak type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin. .

As the phosphorus-containing epoxy resin as the component C, the above-mentioned phosphorus-containing epoxy resin can be used. Further, as the phosphazene-based resin of the component C, the above-mentioned phosphazene-based resin can be used.

As the rubber-modified polyamidoximine resin of the D component, the above-mentioned rubber-modified polyamidoximine resin can be used. As the resin curing agent of the component E, the above-mentioned resin curing agent can be used.

A solvent is added as a resin varnish to the resin composition shown above, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the resin composition, and adjusting the amount of the resin solid content to a range of 30% by weight to 70% by weight. When measured according to MIL-P-13949G in the MIL standard, a resin overflow can be formed (resin Flow) is a semi-hardened resin film in the range of 5% to 35%. As the solvent, a known solvent or the above solvent can be used.

The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer on the surface of the first thermosetting resin layer, and a first thermosetting resin layer. The second thermosetting resin layer may be formed by using a resin component which is insoluble in the chemical treatment of the desmear process in the wiring board manufacturing process, and the second thermosetting resin layer may be a degumming residue which is soluble in the wiring board manufacturing process. The chemical formed by the treatment and the resin formed by washing and removing. The first thermosetting resin layer may be formed by using any one or two or more kinds of resin components in which a polyimine resin, a polyether oxime, or a polyphenylene ether is mixed. The second thermosetting resin layer may be formed by using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is preferably such that the roughened surface roughness of the copper foil with a carrier is Rz (μm) and the thickness of the second thermosetting resin layer is thick. When the degree is set to t2 (μm), t1 satisfies the thickness of the condition of Rz < t1 < t2.

The above resin layer may be a prepreg impregnated with a resin in a skeleton material. The resin impregnated in the above skeleton material is preferably a thermosetting resin. The prepreg may be a prepreg used in the manufacture of a known prepreg or printed wiring board.

The above skeleton material may contain an aromatic polyamide fiber or a glass fiber or a wholly aromatic polyester fiber. The above skeleton material is preferably a non-woven fabric or a woven fabric of an aromatic polyamide fiber or a glass fiber or a wholly aromatic polyester fiber. Further, the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C or higher is a fiber produced by using a resin called a liquid crystal polymer, and the liquid crystal polymer is 2-hydroxy-6-naphthoic acid and p-hydroxy group. The benzoic acid polymer is the main component. Since the wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, it has excellent performance as a constituent material of the electrical insulating layer, and can be used in the same manner as glass fibers and aromatic polyamide fibers.

Further, in order to improve the wettability of the resin on the surface thereof, the fibers constituting the nonwoven fabric and the woven fabric are preferably subjected to a decane coupling agent treatment. In the decane coupling agent at this time, a known amide coupling agent such as an amine group or an epoxy group or the above decane coupling agent may be used depending on the purpose of use.

Further, the prepreg may be impregnated with a thermosetting resin in a skeleton material comprising a non-woven fabric of an aromatic polyamide fiber or a glass fiber having a nominal thickness of 70 μm or less, or a glass cloth having a nominal thickness of 30 μm or less. Prepreg.

(In the case where the resin layer contains a dielectric (dielectric filler))

The above resin layer may contain a dielectric (dielectric filler).

In the case where a dielectric (dielectric filler) is contained in any of the above resin layers or resin compositions, it can be used for the purpose of forming a capacitor layer, and the capacitance of the capacitor circuit is increased. The dielectric (dielectric filler) is BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), PbLaTiO ₃ -PbLaZrO (commonly known as PLZT), and SrBi ₂ Ta ₂ O ₉ (commonly known as SBT). A dielectric powder having a composite oxide having a perovskite structure.

The dielectric (dielectric filler) can be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder characteristics of the dielectric (dielectric filler) must first be such that the particle diameter is from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0. The range of μm. The term "particle size" as used herein refers to an indirect measurement in which the average particle diameter is estimated based on the measured values such as the laser diffraction scattering type particle size distribution measurement method or the BET method. The average particle diameter obtained by image-analyzing the SEM image by directly observing a dielectric (dielectric filler) by a scanning electron microscope (SEM) because it is inferior in accuracy. In the present specification, the particle size at this time is expressed as DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed using a scanning electron microscope (SEM) in the present specification uses IP-1000PC manufactured by Asahi Engineering Co., Ltd. to make roundness. The average particle diameter DIA was determined by setting the threshold value to 10 and the degree of overlap to 20 and performing circular particle analysis.

According to the above embodiment, it is possible to provide a copper foil with a carrier which can improve the adhesion between the surface of the inner layer of the inner core material and the resin layer containing the dielectric, and has a lower content for inclusion. The dielectric loss is tangent to the resin layer of the dielectric of the capacitor circuit layer.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N -methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2- A resin liquid (resin varnish) is prepared by a solvent such as pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, and is coated by, for example, a roll coating method. The B-stage state is formed on the ultra-thin copper layer or the heat-resistant layer, the rust-preventive layer, or the chromate-treated layer or the decane coupling agent layer, followed by heat drying as necessary to remove the solvent. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved in a solvent to obtain a resin solid content of from 3 wt% to 70 wt%, preferably from 3 wt% to 60 wt%, preferably 10 A resin liquid of wt% to 40% by weight, more preferably 25% by weight to 40% by weight. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Further, the resin layer is preferably a semi-cured resin film having a resin overflow rate of 5% to 35% in the measurement according to MIL-P-13949G in the MIL standard.

In the present specification, the term "resin overflow" refers to four pieces of 10 cm square samples taken from a resin-attached copper foil having a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard. In the state in which the samples were overlapped (layered body), the bonding was carried out under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf/cm ² , and a pressing time of 10 minutes, and based on the result of measuring the resin outflow weight at this time, based on the number 1 And calculate the value.

The carrier-attached copper foil (resin-attached copper foil with resin) provided with the above resin layer is used in such a manner that the resin layer is superposed on the substrate and then thermally bonded to the entire resin layer to thermally harden the resin layer, and then the resin layer is thermally cured. The carrier is peeled off to expose an extremely thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the copper foil with a carrier with a resin is used, the number of sheets of the prepreg used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be set to ensure the thickness of the interlayer insulation, or the copper-clad laminate can be produced without using the prepreg material at all. Further, at this time, the insulating resin primer is applied to the surface of the substrate, and the smoothness of the surface can be further improved.

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: only the prepreg material is manufactured. The thickness of the multilayer printed wiring board of the thickness is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 120 μm.

When the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesion is lowered, and when the resin-attached copper foil with a resin is laminated on the substrate having the inner layer material without inserting the prepreg, it is difficult to ensure Interlayer insulation between circuits of the inner layer material. On the other hand, when the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one coating step, and an unnecessary material cost and number of steps are required, which is economically disadvantageous. .

Further, when the copper foil with a carrier layer having a resin layer is used for producing an ultrathin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, and even more preferably When the thickness is from 1 μm to 5 μm, the thickness of the multilayer printed wiring board can be reduced, which is preferable.

Further, when the resin layer contains a dielectric material, the thickness of the resin layer is preferably from 0.1 to 50 μm, preferably from 0.5 μm to 25 μm, more preferably from 1.0 μm to 15 μm.

Further, the total thickness of the resin layer of the cured resin layer and the semi-hardened resin layer is preferably from 0.1 μm to 120 μm, preferably from 5 μm to 120 μm, preferably from 10 μm to 120 μm, more preferably from 10 μm to 60 μm. Further, the thickness of the cured resin layer is preferably from 2 μm to 30 μm, preferably from 3 μm to 30 μm, more preferably from 5 to 20 μm. Further, the thickness of the semi-hardened resin layer is preferably from 3 μm to 55 μm, preferably from 7 μm to 55 μm, more preferably from 15 to 115 μm. The reason for this is that when the total thickness of the resin layer exceeds 120 μm, it is difficult to produce an extremely thin multilayer printed wiring board. If it is less than 5 μm, it may be as follows: although an extremely thin multilayer printed wiring board is easily formed, it may be generated. The insulating layer between the circuits of the layer, that is, the resin layer, becomes too thin, and the insulation between the circuits of the inner layer tends to be unstable. Further, when the thickness of the cured resin layer is less than 2 μm, it is necessary to consider the surface roughness of the roughened surface of the copper foil. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect of the resin layer which is cured by hardening is not particularly improved, and the total thickness of the insulating layer is increased.

Further, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with a carrier, it is preferable to provide a heat-resistant layer on the ultra-thin copper layer and/or After the rustproof layer and/or the chromate treatment layer and/or the decane coupling treatment layer, the heat resistant layer A resin layer is formed on the rustproof layer or the chromate treatment layer or the decane coupling treatment layer.

Furthermore, the thickness of the above resin layer means the average value of the thickness measured by an arbitrary 10-point observation profile.

Further, as another form of the resin-attached copper foil with a resin, a resin layer may be coated on the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromate-treated layer, or After the decane coupling treatment layer was in a semi-hardened state, the carrier was subsequently peeled off and produced in the form of a resin-attached copper foil in the absence of a carrier.

<6. Printed wiring board>

Hereinafter, an example of a manufacturing procedure of a plurality of printed wiring boards using the surface-treated copper foil or the copper foil with a carrier of the present invention will be described. Moreover, the printed circuit board is completed by mounting electronic components on the printed wiring board.

Through the above-described process, a copper foil with a carrier which is provided with a copper foil carrier, a peeling layer and an extremely thin copper layer in this order is manufactured. The method of using the carrier copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth. - Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin, glass cloth substrate, epoxy resin, polyester film, polyimide film, etc. After the carrier is formed, the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern to form a printed wiring board.

The copper foil with a carrier of the present invention is suitable for forming a fine pitch printed wiring board. For example, by using the copper foil with a carrier of the present invention, a printed wiring board having an insulating substrate and a copper circuit provided on the insulating substrate can be manufactured, and the circuit width of the copper circuit is less than 20 μm. The gap width between the copper circuits is less than 20 μm. Further, a printed wiring board having a circuit width of 17 μm or less and a gap width between adjacent copper circuits of 17 μm or less can be manufactured. Further, a printed wiring board having a circuit width of 15 μm or less and a gap width between adjacent copper circuits of 15 μm or less can be manufactured. Furthermore, it can also be manufactured The copper circuit has a circuit width of 5 to 10 μm, and a printed wiring board having a gap width between adjacent copper circuits of 5 to 10 μm.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. By using the copper foil with a carrier of the present invention, for example, a printed circuit board having an insulating substrate and a copper circuit provided on the insulating substrate, wherein the circuit width of the copper circuit is less than 20 μm, can be manufactured The gap width between the copper circuits is less than 20 μm. Further, it is also possible to manufacture a printed circuit board having a circuit width of 17 μm or less and a gap width between adjacent copper circuits of 17 μm or less. Further, a printed wiring board having a circuit width of 17 μm or less and a gap width between adjacent copper circuits of 17 μm or less can be manufactured. Further, it is also possible to manufacture a printed circuit board having a circuit width of 15 μm or less and a gap width between adjacent copper circuits of 15 μm or less. Further, the copper circuit may have a circuit width of 5 to 10 μm, preferably 5 to 9 μm, more preferably 5 to 8 μm, and a gap width between adjacent copper circuits of 5 to 10 μm, preferably 5 to 9 μm. More preferably, it is a printed circuit board of 5 to 8 μm. Further, the distance between the line and the gap is preferably less than 40 μm, more preferably 34 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less, still more preferably 15 μm or less. Further, the lower limit of the line and the gap need not be specifically defined, and is, for example, 6 μm or more, or 8 μm or more, or 10 μm or more.

Furthermore, the distance between the line and the gap refers to the distance from the center of the width of the copper circuit to the center of the width of the adjacent copper circuit.

Hereinafter, an example of a manufacturing procedure of a printed wiring board using the copper foil with a carrier of the present invention will be described.

An embodiment of the method for producing a printed wiring board according to the present invention comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate; and forming a very thin copper After the layer side and the insulating substrate face each other, the copper foil with the carrier and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then, by a semi-additive method ( Semi-additive method The step of forming a circuit by any one of a modified semi-additive method, a partial additive method, and a subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, and a pattern is formed, and a conductor pattern is formed by plating and etching.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the ultra-thin copper exposed by peeling off the carrier by etching or plasma using an etching solution such as acid or the like is used. a step of completely removing the layer; a step of providing a via hole or/and a blind via on the resin layer and the insulating substrate exposed by etching to remove the ultra-thin copper layer; and including the above-mentioned via hole or/and blind a step of removing the slag treatment in the region of the hole; a step of providing an electroless plating layer in the resin and the region including the through hole or/and the blind hole; and a step of providing a plating resist on the electroless plating layer And exposing the above-mentioned anti-plating agent, and thereafter, removing the anti-plating agent in the region where the circuit is formed; and providing electrolytic plating in a region where the above-mentioned circuit is formed by removing the anti-plating agent The step; plating resist removing the cataplasm of step; and The step of removing the electroless plating layer in the region other than the region in which the above-described circuit is formed by flash etching or the like.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the carrier is peeled off by etching or plasma using an etching solution such as acid. a step of completely removing the copper layer; a step of providing an electroless plating layer on the surface of the resin layer exposed by removing the ultra-thin copper layer by etching; and a step of providing a plating resist on the electroless plating layer; a step of exposing the above-mentioned anti-plating agent, and then removing the anti-plating agent in the region where the circuit is formed; and removing the anti-plating agent to form an electrolytic plating layer in the region where the circuit is formed; The step of resisting the plating agent; and the step of removing the electroless plating layer in a region other than the region in which the circuit is formed by flash etching or the like.

In the present invention, the modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and etching the copper layer of the circuit forming portion to remove the resist. A method of forming a circuit on an insulating layer by (fast) etching to remove a metal foil other than the above-described circuit forming portion.

Therefore, a method of manufacturing a printed wiring board of the present invention using a modified semi-additive method An embodiment includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the insulating substrate a step of peeling off the carrier with the carrier copper foil; a step of providing a through hole or/and a blind hole in the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; and removing the region including the through hole or/and the blind hole a step of treating a slag; a step of providing an electroless plating layer in a region including the through hole or/and the blind hole; and a step of providing a plating resist on a surface of the extremely thin copper layer exposed by peeling the carrier; a step of forming a circuit by electroplating after the plating resist; a step of removing the anti-plating agent; and a step of removing an extremely thin copper layer exposed by removing the anti-plating agent by flash etching.

Another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier-attached copper foil carrier after laminating the carrier-attached copper foil and the insulating substrate; and providing a plating resist on the extremely thin copper layer exposed by peeling off the carrier; a step of exposing the plating agent, thereafter removing the anti-plating agent in the region where the circuit is formed; and disposing the electroplating layer in the region where the anti-plating agent is removed to form the circuit; removing the anti-plating The step of applying the agent; and The step of removing an extremely thin copper layer in a region other than the region in which the above-described circuit is formed by flash etching or the like.

In the present invention, the partial addition method refers to a substrate in which a conductor layer is provided, a catalyst core is provided on a substrate through which a hole for a via hole or a via hole is required to be formed, and etching is performed to form a conductor circuit. After the solder resist or the anti-plating agent is provided as needed, a via hole, a via hole, or the like is thickened on the conductor circuit by electroless plating to form a printed wiring board.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a partial addition method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier, and providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier a step of performing desmear treatment on a region including the through hole or/and the blind hole; a step of imparting a catalyst core to a region including the through hole or/and the blind hole; and exposing the carrier by peeling off the carrier a step of providing an anti-etching agent on the surface of the thin copper layer; a step of exposing the anti-etching agent to form a circuit pattern; removing the ultra-thin copper layer and the above-mentioned catalyst by etching or plasma using an etching solution such as acid a step of forming a circuit; a step of removing the above-mentioned anti-etching agent; removing the above-mentioned ultra-thin copper layer and the above-mentioned catalyst core by etching or plasma using an etching solution having an acid or the like Exposed on the surface of the insulating substrate, a solder resist is provided cataplasm or steps of plating resist; and is not provided to the above-described solder resist or an anti-plating agent coated region setting step of electroless plating layers.

In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like.

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate After laminating the carrier-attached copper foil and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the through-hole or/and the blind via are provided on the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier. a step of performing desmear treatment on a region including the through hole or/and the blind hole; a step of providing an electroless plating layer in a region including the through hole or/and the blind hole; and the electroless plating layer a step of providing an electrolytic plating layer on the surface; a step of providing an anti-etching agent on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; exposing the etching resist to form a circuit pattern; a step of forming an electric circuit by etching or plasma etching or the like to remove the ultra-thin copper layer and the electroless plating layer and the electroless plating layer; and removing the anti-etching agent .

Another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the carrier and the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; and the through-hole or/and the blind via are provided on the extremely thin copper layer and the insulating substrate which are exposed by peeling off the carrier. a step of performing desmear treatment on a region including the through hole or/and the blind hole; a step of providing an electroless plating layer in a region including the through hole or/and the blind hole; and the electroless plating layer a step of forming a mask on the surface; a step of providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed; and an anti-etching agent on the surface of the electrolytic plating layer or/and the ultra-thin copper layer a step of exposing the anti-etching agent to form a circuit pattern; removing the ultra-thin copper layer and the electroless plating layer by etching or plasma using an etching solution such as an acid to form a circuit a step; and a step of removing the above etch resist.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Here, the copper foil with a carrier having an ultra-thin copper layer in which a roughened layer is formed is exemplified, but the invention is not limited thereto, and an ultrathin copper layer having a roughened layer is not used. The carrier copper foil can also be similarly produced by the following method of manufacturing a printed wiring board.

First, as shown in FIG. 3-A, a copper foil with a carrier (first layer) having an extremely thin copper layer having a roughened layer formed on its surface is prepared.

Next, as shown in FIG. 3-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a specific shape.

Then, as shown in FIG. 3-C, after the plating for forming the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Then, as shown in FIG. 4-D, a resin layer is deposited on the ultra-thin copper layer by plating the coated circuit (by plating the buried circuit), and then the resin layer is laminated on the side of the ultra-thin copper layer. Another carrier copper foil (layer 2).

Then, as shown in Fig. 4-E, the carrier was peeled off from the carrier copper foil of the second layer.

Then, as shown in FIG. 4-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating to form a blind hole.

Then, as shown in FIG. 5-G, a hole filled with copper is formed in the blind hole.

Then, as shown in FIG. 5-H, circuit plating is formed on the filling holes in the manner of FIG. 3-B and FIG. 3-C described above.

Then, as shown in Fig. 5-I, the carrier was peeled off from the carrier copper foil of the first layer.

Then, as shown in Fig. 6-J, the extremely thin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Then, as shown in Fig. 6-K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier copper foil (second layer) can be used with the copper foil with a carrier of the present invention, and a conventional copper foil with a carrier can be used, and a usual copper foil can also be used. Further, a layer 1 or a plurality of layers may be further formed on the circuit of the second layer shown in FIG. 5-H, which may be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method forms the circuits.

Further, the copper foil with a carrier used for the first layer described above may have a substrate on the side of the carrier side of the copper foil with a carrier. By having such a substrate or a resin layer, the copper foil with a carrier for the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, as long as the substrate has an effect of supporting the above-described copper foil with a carrier for the first layer, all of the substrates can be used. For example, a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, or a plate of an organic compound, which are described in the present specification, may be used. A foil of an organic compound is used as the above substrate.

The time at which the substrate is formed on the side surface of the carrier is not particularly limited, but it must be formed before the carrier is peeled off. In particular, it is preferable that the above-mentioned ultra-thin copper layer side surface of the above-mentioned copper foil with a carrier It is formed before the step of forming the resin layer, and is preferably formed before the step of forming a circuit on the side surface of the above-mentioned ultra-thin copper layer of the carrier copper foil.

The copper foil with a carrier of the present invention preferably controls the chromatic aberration of the surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the present invention, the "chromatic aberration of the surface of the ultra-thin copper layer" means the chromatic aberration of the surface of the ultra-thin copper layer or the chromatic aberration of the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably controls the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling layer in such a manner as to satisfy the following (1). Color difference.

(1) The color difference ΔE* ab based on JIS Z8730 of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the decane coupling treatment layer is 45 or more.

Here, the color difference ΔL, Δa, and Δb are measured by a color difference meter, and black/white/red/green/yellow/blue is used, and a comprehensive index expressed by the L*a*b color system based on JISZ8730 is used. And expressed as ΔL: white black, Δa: red green, △ b: yellow blue. Further, ΔE* ab is expressed by the following formula using these chromatic aberrations.

The chromatic aberration can be adjusted by increasing the current density at the time of formation of the ultra-thin copper layer, lowering the concentration of copper in the plating solution, and increasing the linear flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by performing a roughening treatment on the surface of the ultra-thin copper layer and providing a roughened layer. In the case where the roughening treatment layer is provided, it is possible to further increase the current density by using an electric field liquid containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum (for example, 40~) 60A/dm ² ), the processing time is shortened (for example, 0.1 to 1.3 seconds) and adjusted. In the case where the roughened layer is not provided on the surface of the ultra-thin copper layer, it can be achieved by using a plating bath having a concentration of Ni twice or more of other elements, and a very thin copper layer or a heat-resistant layer. Or the surface of the rustproof layer or the chromate treatment layer or the decane coupling treatment layer to make the Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) low The processing is performed in a manner of a conventional current density (0.1 to 1.3 A/dm ² ) and a long processing time (20 seconds to 40 seconds).

When the color difference ΔE* ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer with the carrier copper foil, the contrast between the ultra-thin copper layer and the circuit becomes clear, and the result is visually recognized. The performance is good, and the positional alignment of the circuit can be performed with high precision. The color difference ΔE* ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the chromatic aberration of the surface of the ultra-thin copper layer or the roughened layer or the heat-resistant layer or the rust-proof layer or the chromate-treated layer or the decane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear, Visual recognition has become good. Therefore, in the manufacturing steps shown in, for example, FIG. 3-C of the printed wiring board as described above, the circuit plating can be formed accurately at a specific position. Further, according to the method for manufacturing a printed wiring board as described above, a structure in which a circuit layer is embedded in a resin layer is formed. Therefore, for example, when a very thin copper layer is removed by flash etching as shown in FIG. 6-J, The layer protection circuit is plated and maintained in shape, whereby it is easy to form a fine circuit. Moreover, since the plating is protected by the resin layer protection circuit, the migration resistance is improved, and the wiring of the circuit can be satisfactorily suppressed. Therefore, it is easy to form a fine circuit. Further, when the ultra-thin copper layer is removed by flash etching as shown in FIGS. 6-J and 6-K, the exposed surface of the circuit plating becomes a shape recessed from the resin layer, so that it is easy to separate the circuit plating. The bumps are formed and a copper pillar is formed thereon, and the manufacturing efficiency is improved.

Further, a well-known resin or prepreg can be used as the resin (Resin). For example, a BT (Bismaleimide) resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF can be used. Further, as the above-mentioned embedded resin (Resin), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples of the invention, but The invention is not limited by the examples.

1. Manufacture of carrier copper foil

<Example 1>

As the copper foil carrier, a long strip of electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm was prepared. The shiny surface (Rz: 1.2 to 1.4 μm) of the copper foil is electroplated by a roll-to-roll continuous plating line (bending method shown in Fig. 2) under the following conditions. A Ni layer of 4000 μg/dm ² adhesion was formed.

. Ni layer

Nickel sulfate: 250~300g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

After washing with water and pickling, the Cr layer of 11 μg/dm ² is subjected to electrolytic chromic acid under the following conditions by means of a roll-to-roll continuous plating line (using the bending method shown in Fig. 2). The salt is treated to adhere to the Ni layer.

. Electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

Then, by the roll-to-roll continuous plating line (using the drum method shown in FIG. 1), an ultra-thin copper layer having a thickness of 3 μm is plated on the Cr layer under the following conditions to form an attached layer. Carrier copper foil. Further, in this example, a copper foil with a carrier having an extremely thin copper layer of 1, 2, 5, or 10 μm was also produced, and the same evaluation was carried out for an example in which the thickness of the ultra-thin copper layer was 3 μm. The results are the same regardless of the thickness.

. Very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20~120g/L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

Then, the surface of the ultra-thin copper layer is sequentially subjected to the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and decane coupling treatment. The roughening treatment 1 and the roughening treatment 2 are carried out by using the foil transfer method shown in Fig. 1 (the distance between the poles is 50 mm), and the rust prevention treatment, the chromate treatment, and the decane coupling treatment are performed by the bending shown in Fig. 2. the way.

. Coarsening treatment 1

(liquid composition 1)

Cu: 10~30g/L

_{H 2 SO 4: 10 ~ 150g} / L

W: 0~50mg/L

Sodium lauryl sulfate: 0~50mg/L

As: 0~200mg/L

(plating condition 1)

Temperature: 30~70°C

Current density: 25~110A/dm ²

Coarse coulomb amount: 50~500As/dm ²

Plating time: 0.5~20 seconds

. Coarsening treatment 2

(liquid composition 2)

Cu: 20~80g/L

H ₂ SO ₄ : 50~200g/L

(plating condition 2)

Temperature: 30~70°C

Current density: 5~50A/dm ²

Coarse coulomb amount: 50~300As/dm ²

Plating time: 1~60 seconds

. Anti-rust treatment

(liquid composition)

NaOH: 40~200g/L

NaCN: 70~250g/L

CuCN: 50~200g/L

Zn(CN) ₂ : 2~100g/L

As ₂ O ₃ : 0.01~1g/L

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

. Chromate treatment

K ₂ Cr ₂ O ₇ (N _a2 Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnOH or ZnSO ₄ . 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

. Decane coupling treatment

0.1 to 30% by volume of an aqueous solution of 3-glycidoxypropyltrimethoxydecane is spray-coated, and then dried in an air of 100 to 200 ° C for 0.1 to 10 seconds.

After the surface treatment described above, the resin layer of the following "A" was formed on the side of the ultra-thin copper layer.

<Example 2>

After forming an extremely thin copper layer on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and decane coupling treatment were sequentially performed. The roughening treatment 1 and the roughening treatment 2 are carried out by using the foil transfer method shown in Fig. 1 (the distance between the poles is 50 mm), and the rust prevention treatment, the chromate treatment, and the decane coupling treatment are performed by the bending shown in Fig. 2. the way. Further, the thickness of the ultra-thin copper foil was set to 3 μm.

. Coarsening treatment 1

Liquid composition: copper 10~20g/L, sulfuric acid 50~100g/L

Liquid temperature: 25~50°C

Current density: 1~58A/dm ²

Coulomb amount: 4~81As/dm ²

. Coarsening treatment 2

Liquid composition: copper 10~20g/L, nickel 5~15g/L, cobalt 5~15g/L

pH: 2~3

Liquid temperature: 30~50°C

Current density: 24~50A/dm ²

Coulomb amount: 34~48As/dm ²

. Anti-rust treatment

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

. Chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (for impregnation of chromate, it can also be carried out without electrolysis)

Coulomb amount: 0~2As/dm ² (for impregnation of chromate treatment, it can also be carried out without electrolysis)

. Decane coupling treatment

Coating of diamino decane aqueous solution (diamine decane concentration: 0.1 to 0.5 wt%)

After the surface treatment described above, the resin layer of the following "B" was formed on the side of the ultra-thin copper layer.

<Example 3>

A long strip of electrolytic copper foil (HLP manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm was prepared as a copper foil carrier, and the shiny surface (Rz: 0.1 to 0.3 μm) of the copper foil was the same as in Example 1. The carrier copper foil was prepared in sequence. Among them, the resin layer forms the following "C".

<Example 4>

As a copper foil carrier, prepare a strip of electrolytic copper foil with a thickness of 35 μm (JX Nippon Mining & Metal Co., Ltd.) HLP manufactured by the company, a copper foil with a carrier was prepared in the same manner as in Example 2 on the shiny side (Rz: 0.1 to 0.3 μm) of the copper foil. Among them, the resin layer forms the following "D".

<Example 5>

As the copper foil carrier, a long strip of electrolytic copper foil (HLP manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm was prepared. Under the same conditions as in Example 1, the shiny side (Rz: 0.1 to 0.3 μm) of the copper foil was plated by a roll-to-roll type continuous plating line, thereby forming a Ni layer of 4000 μg/dm ² adhesion amount. Then, after forming an ultra-thin copper layer in the same order as in the first embodiment, the following anti-rust treatment (using a bending method) was carried out without performing the roughening treatment.

. Anti-rust treatment

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

After the surface treatment described above, a resin layer of the following "E" was formed on the side of the ultra-thin copper layer.

<Comparative Example 1>

After forming an extremely thin copper layer on the copper foil carrier under the same conditions as in Example 1, the surface of the ultra-thin copper layer was sequentially subjected to the following roughening treatment 1, roughening treatment 2, rust prevention treatment, and chromic acid. Salt treatment and decane coupling treatment. The roughening treatment 1 and the roughening treatment 2 are carried out by using the foil transfer method shown in Fig. 1 (the distance between the poles is 50 mm), and the rust prevention treatment, the chromate treatment, and the decane coupling treatment are performed by the bending shown in Fig. 2. the way. Further, the thickness of the ultra-thin copper foil was set to 3 μm.

. Coarsening treatment 1

(liquid composition 1)

Cu: 31~45g/L

_{H 2 SO 4: 10 ~ 150g} / L

As: 0.1~200mg/L

(plating condition 1)

Temperature: 30~70°C

Current density: 25~110A/dm ²

Coarse coulomb amount: 50~500As/dm ²

Plating time: 0.5~20 seconds

. Coarsening treatment 2

(liquid composition 2)

Cu: 20~80g/L

H ₂ SO ₄ : 50~200g/L

(plating condition 2)

Temperature: 30~70°C

Current density: 5~50A/dm ²

Coarse coulomb amount: 50~300As/dm ²

Plating time: 1~60 seconds

. Anti-rust treatment

(liquid composition)

NaOH: 40~200g/L

NaCN: 70~250g/L

CuCN: 50~200g/L

Zn(CN) ₂ : 2~100g/L

As ₂ O ₃ : 0.01~1g/L

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

. Chromate treatment

K ₂ Cr ₂ O ₇ (N _a2 Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnOH or ZnSO ₄ . 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

. Decane coupling treatment

0.1 to 30% by volume of an aqueous solution of 3-glycidoxypropyltrimethoxydecane is spray-coated, and then dried in an air of 100 to 200 ° C for 0.1 to 10 seconds.

After the surface treatment described above, no resin layer was formed.

<Comparative Example 2>

The roughening treatment 1 and the roughening treatment 2 were carried out in the same manner as in Example 1 except that the foil-forming method by bending was used as shown in Fig. 2 . However, no resin layer was formed.

<Comparative Example 3>

The roughening treatment 1 and the roughening treatment 2 were carried out in the same manner as in Example 2 except that the foil-forming method by bending was used as shown in Fig. 2 . However, no resin layer was formed.

<Comparative Example 4>

The following resin layer "A" was formed on the extremely thin copper layer side of the carrier copper foil of Comparative Example 1.

<Comparative Example 5>

The following resin layer "B" was formed on the extremely thin copper layer side of the copper foil with a carrier of Comparative Example 2.

<Comparative Example 6>

The following resin layer "C" was formed on the extremely thin copper layer side of the carrier copper foil of Comparative Example 3.

<Example 6>

A copper foil with a carrier was produced in the same manner as in Example 1 except that the resin layer was not formed.

<Example 7>

A copper foil with a carrier was produced in the same manner as in Example 2 except that the resin layer was not formed.

<Example 8>

A copper foil with a carrier was produced in the same manner as in Example 3 except that the resin layer was not formed.

<Example 9>

A copper foil with a carrier was produced in the same manner as in Example 4 except that the resin layer was not formed.

<Example 10>

A copper foil with a carrier was produced in the same manner as in Example 5 except that the resin layer was not formed.

<Formation of Resin Layer>

The formation of the resin layer is carried out in the following manner.

. "A"

(Resin Synthesis Example)

Adding 3,4/3',4'-biphenyl to a 2-liter three-necked flask equipped with a reflux condenser with a spherical condenser on a stainless steel crucible stir bar, a nitrogen gas inlet pipe, and a plug that stops the plug 117.68 g (400 mmol) of tetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis(3-aminophenoxy)benzene, 4.0 g (40 mmol) of γ-valerolactone, and 4.8 g (60 mmol) of pyridine. 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were heated at 180 ° C for 1 hour, then cooled to near room temperature, and then added 3,4/3'4'-linked. Benzenetetracarboxylic dianhydride 29.42g (100mmol), 2,2-bis{4-(4-aminophenoxy)phenyl}propane 82.12g (200mmol), NMP 200g, and toluene 40g at room temperature After mixing for 1 hour, it was heated at 180 ° C for 3 hours to obtain a block copolymerized polyimine of 38% of a solid content. In the block copolymerized polyimine, the general formula (1) represented by the following formula: (2) = 3:2, the number average molecular weight: 70,000, and the weight average molecular weight: 150,000.

The block copolymerized polyimine solution obtained in the synthesis example was further diluted with NMP to prepare a block copolymerized polyimine solution having a solid content of 10%. In the block copolymerized polyimine solution, the solid content ratio of bis(4-maleimidophenyl)methane (BMI-H, KI Chemical Industry) is 35, block copolymerization poly Amine solid component weight ratio 65 (ie, bis(4-maleimidophenyl)methane solid content component contained in the resin solution: block copolymerized polyimine solid content contained in the resin solution The form of the component weight = 35:65) was dissolved and mixed at 60 ° C for 20 minutes to prepare a resin solution. Thereafter, the resin solution was applied to the side surface of the ultra-thin copper layer of the copper foil with a carrier before the resin layer was placed using a reverse roll coater, and dried at 120 ° C for 3 minutes under nitrogen atmosphere at 160 ° C. After drying for 3 minutes, the heat treatment was finally carried out at 300 ° C for 2 minutes to prepare a copper foil with a carrier. Further, the thickness of the resin layer was set to 2 μm.

. "B"

B is a resin composition in which 69 parts by weight of an epoxy resin, 11 parts by weight of a curing agent, 0.25 parts by weight of a curing accelerator, 15 parts by weight of a polymer component, 3 parts by weight of a crosslinking agent, and 3 parts by weight of a rubber resin are prepared.

Specifically, it is expressed as follows.

[Composition of Resin Composition]

Component/specific component/specific chemical name (manufacturing company)/composition (parts by weight)

Epoxy resin / bisphenol A type / YD-907 (made by Tohto Kasei) / 15

Epoxy resin / bisphenol A type / YD-011 (made by Toshiro Kasei) / 54

Hardener / Aromatic Amine / 4,41-Diaminodiphenyl hydrazine (made by Wakayama Seiki) / 12

Hardening accelerator / imidazole / 2E4MZ (manufactured by Shikoku Kasei) / 0.4

Polymer composition / polyvinyl acetal resin / 5000A (manufactured by Electrical and Chemical Industry) / 15

Crosslinking agent / urethane resin / AP-Stable (manufactured by Nippon Polyurethane) / 3

Rubber component / core shell type nitrile rubber / XER-91 (manufactured by JSR) / 3

Then, the resin composition shown above was adjusted to 30% by weight using methyl ethyl ketone and dimethyl acetamide to prepare a resin composition solution for forming a resin layer. Then, the resin composition solution for forming a resin layer was applied to the surface of the ultra-thin copper layer side of the copper foil with a carrier before the resin layer was formed using a gravure coater. Then, it was air-dried for 5 minutes, and thereafter, it was dried in a heating environment of 140 ° C for 3 minutes to form a semi-hardened resin layer (adhesive layer) having a thickness of 1.5 μm in a semi-hardened state, thereby producing a copper foil with a carrier. The resin overflow amount of the semi-hardened resin layer (adhesive layer) obtained at this time was measured by using a resin composition for forming a resin layer to form a semi-hardened resin layer of 40 μm thick on one side of a copper foil having a thickness of 18 μm. Then, it is set as a sample for resin overflow flow measurement. Then, four sheets of 10 cm square samples were taken from the resin overflow flow measurement sample, and the resin overflow flow rate was measured in accordance with the above MIL-P-13949G. As a result, the resin overflow rate was 1.5%.

. "C"

A resin solution constituting the resin layer is produced. In the production of the resin solution, an epoxy resin (EPPN-502 manufactured by Nippon Kayaku Co., Ltd.) and a polyether oxime resin (Sumikaexcel PES-5003P manufactured by Sumitomo Chemical Co., Ltd.) were used as a raw material. Then, an imidazole-based 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator was added thereto to prepare a resin composition.

Resin composition: 50 parts by weight of epoxy resin

50 parts by weight of polyether oxime resin

Hardening accelerator 1 part by weight

The resin composition was further adjusted to 30% by weight of the resin solid content using dimethylformamide to prepare a resin solution. The resin solution produced in the above manner was applied to the surface of the extremely thin copper layer side of the copper foil with a carrier before the resin layer was formed using a gravure coater. Then, it was dried in a heating environment of 140 ° C for 3 minutes to form a resin layer of 1.5 μm thick in a semi-hardened state, and the copper foil with a carrier of the present invention was obtained. On the other hand, in order to measure the resin overflow amount, a resin-coated copper foil (copper foil thickness: 18 μm) having a primer resin layer of 40 μm thick (hereinafter referred to as "resin overflow measurement sample") was produced. Then, four pieces of 10 cm square samples were taken from the resin overflow flow measurement sample, and the resin overflow flow rate was measured based on the above-mentioned MIL-P-13949G. As a result, the resin overflow rate was 1.4%.

. "D"

The surface of the ultra-thin copper layer of the copper foil with a carrier before the resin layer is provided to form a polyimide resin layer as a hardened resin layer, and the semi-hardened resin layer is formed by using a copper carrier with a maleic amide resin. An example of foil.

Preparation of Polyamic Acid Varnish: A polyamic acid varnish for forming a hardened resin layer by a casting method will be described. 1 mol of pyromellitic dianhydride and 1 mol of 4,4'-diaminodiphenyl ether were dissolved in N-methylpyrrolidone as a solvent, and they were mixed. The reaction temperature at this time was 25 ° C, and the reaction was carried out for 10 hours. Then, a polyamic acid varnish having a resin solid content of 20% by mass was obtained.

Formation of a hardened resin layer: Then, using the obtained polyamic acid varnish, a hardened resin layer was formed by a casting method. The polyphthalic acid varnish was applied to the side surface of the ultra-thin copper layer of the copper foil with a carrier before the resin layer was set by Multi Coater (manufactured by Hirano Tecseed Co., Ltd.: M-400) in a hot air dryer at 110 ° C Drying was carried out for 6 minutes. The resin thickness of the dried hardened resin layer is set to 35 μm, and the solvent residual ratio at this stage is relative to the total amount of the resin layer. It is 32% by weight. The composite of the electrolytic copper foil coated with the polyamic acid varnish was placed in a hot air oven substituted with nitrogen, and the temperature was raised from room temperature to 400 ° C over 15 minutes, and then maintained at 400 ° C for 8 minutes. cool down. Thereby, the residual solvent is removed from the composite with the carrier-coated copper foil coated with poly-proline, and the polyacrylic acid is subjected to a dehydration ring-closing ruthenium imine reaction to prepare a copper foil with a carrier. A copper-clad polyimide substrate having a state in which a thin copper layer side surface layer has a cured resin layer. The solvent residual ratio of the copper-clad polyimide film substrate obtained by the final heat treatment was 0.5% by weight based on the total amount of the resin attached to the copper foil with a carrier.

Then, the carrier-attached copper foil (copper-coated polyimine resin substrate) in which the hardened resin layer is laminated is subjected to corona treatment, and the surface of the cured resin layer is modified. Corona treatment is in the atmosphere, power 210W, speed 2m / min, discharge capacity 300W. The temperature is min/m ² and the irradiation distance of the electrode is 1.5 mm. Further, in order to measure the thermal expansion coefficient of the cured resin layer, the copper-attached copper foil (corona-treated copper-coated polyimide substrate) obtained by laminating the hardened resin layer after the surface modification treatment The foil is peeled off and etched to remove it. As a result, the cured resin layer (polyimine film) obtained by removing the copper foil with a carrier had a resin thickness of 27 μm and a thermal expansion coefficient of 25 ppm/°C.

Formation of semi-hardened resin layer: Here, a semi-hardened resin layer is formed on the hardened resin layer of the copper-clad polyimide film substrate which is subjected to corona treatment. First, the resin composition shown below was dissolved using N,N'-dimethylacetamide as a solvent to prepare a resin varnish having a resin solid content of 30% by weight.

[Resin composition forming a semi-hardened resin layer]

Maleic imine resin: 4,4'-diphenylmethane bismaleimide (trade name: BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) / 30 parts by weight

Aromatic polyamine resin: 1,3-bis[4-aminophenoxy]benzene (trade name: TPE-R, manufactured by Wakayama Seiki Co., Ltd.) / 35 parts by weight

Epoxy resin: bisphenol A type epoxy resin (trade name: EPICLON 850S, Dainippon ink) Manufactured by Chemical Industry Co., Ltd.) / 20 parts by weight

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: Denka Butyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 15 parts by weight

The resin varnish was applied to the surface of the polyacrylonitrile resin substrate of the corona-treated copper-polyimide resin substrate, and air-dried at room temperature for 5 minutes, and heated at 160 ° C for 5 minutes. Dry and laminate to form a semi-hardened resin layer. The resin thickness of the semi-hardened resin layer at this time was set to 20 μm.

Further, in order to measure the thermal expansion coefficient of the semi-hardened resin layer after curing, the above-mentioned resin varnish for forming a semi-hardened resin layer is applied to a fluorine-based heat-resistant film by the same method as described above, and air-dried at room temperature for 5 minutes. The film was dried by heating at 160 ° C for 5 minutes, and further subjected to hardening heating at 200 ° C for 2 hours to obtain a test cured resin layer having a thickness of 20 μm. That is, the test cured resin layer corresponds to the case where the semi-hardened resin layer of the copper foil with a carrier of the present invention is cured. The test cured resin layer had a coefficient of thermal expansion of 45 ppm/°C.

The thickness of the entire resin layer of the copper foil with a carrier obtained in the above manner was 47 μm. Further, the copper foil was removed by etching from the resin-coated copper foil, and a resin layer composed of a cured resin layer and a semi-hardened resin layer was used, and it was subjected to hardening heating at 200 ° C for 2 hours, and the measurement was performed. The coefficient of thermal expansion of the entire resin layer after the semi-hardened resin layer is hardened. As a result, the coefficient of thermal expansion was 35 ppm/°C. Further, the peel strength was 1.0 kgf/cm.

. "E"

First, the first resin composition constituting the resin layer was produced. In the production of the first resin composition, an o-cresol novolac type epoxy resin (YDCN-704 manufactured by Tohto Kasei Co., Ltd.), a solvent-soluble aromatic polyamide resin polymer, and As a mixed varnish of cyclopentanone as a solvent, BP3225-50P manufactured by Nippon Kayaku Co., Ltd., which is commercially available, is used as a raw material. In addition, VH-4170 manufactured by Dainippon Ink Co., Ltd. and 2E4MZ manufactured by Shikoku Kasei Co., Ltd., which is a hardening accelerator, are added to the phenolic resin as a curing agent. A first resin composition having a blending ratio shown below was prepared in the mixed varnish.

O-cresol novolak type epoxy resin 38 parts by weight

Aromatic polyamide resin polymer 50 parts by weight

Phenolic resin 18 parts by weight

Hardening accelerator 0.1 parts by weight

The resin composition was further prepared by further adjusting the resin solid content to 30% by weight of the first resin composition using methyl ethyl ketone.

The side surface of the extremely thin copper layer of the copper foil with a carrier before the formation of the resin layer (the surface treated surface in the case of surface treatment of the ultra-thin copper layer) is immersed in a concentration of 5 g/l. A solution obtained by adding γ-glycidoxypropyltrimethoxydecane to ion-exchanged water was subjected to a sorption treatment. Then, the inside of the furnace was adjusted to a temperature of 180 ° C by an electric heater to release moisture, and a condensation reaction of a decane coupling agent was carried out to form a decane coupling agent layer.

The resin solution produced in the above manner was applied to the surface of the decane coupling agent layer on which the carrier-attached copper foil was formed using a gravure coater. Then, it was air-dried for 5 minutes, and then dried in a heating environment of 140 ° C for 3 minutes to form a resin layer of 1.5 μm thick in a semi-hardened state, thereby obtaining a copper foil with a carrier of the present invention. In the measurement of the resin overflow flow rate, a resin-coated copper foil having a thickness of 40 μm in the undercoat resin layer (hereinafter referred to as "resin overflow measurement sample") was produced.

Further, four 10 cm square samples were taken from the resin overflow flow measurement sample, and the resin overflow flow rate was measured in accordance with the above MIL-P-13949G. As a result, the resin overflow rate was 1.5%.

2. Evaluation of the characteristics of copper foil with carrier

The characteristic evaluation of the copper foil with a carrier obtained as above was performed by the following method. The results are shown in Table 1. In addition, "3.91E-16" of "Ra" in the "standard deviation (μm) column" of Table 1 indicates 3.19 × 10 ^-16 (μm), and "1.30E-02" indicates 1.30 × 10 ^-2 ( Mm).

(Surface roughness)

Each of the carrier-attached copper foils (squares of 550 mm × 550 mm) before the formation of the resin layer was linearly drawn at a pitch of 55 mm in the longitudinal direction, and 100 portions of each of the squares of 55 mm × 55 mm were allocated. A contact roughness measuring machine (Surfcorder SE-3C manufactured by Kosaka Research Co., Ltd.) was used for each area, and the following were based on JIS B0601-1982 (Ra, Rz) and JIS B0601-2001 (Rt). The surface roughness (Ra, Rt, Rz) of the ultra-thin copper layer was measured under the measurement conditions, and the average value and standard deviation were measured.

<Measurement conditions>

Cut-off point: 0.25mm

Base length: 0.8mm

Determination of ambient temperature: 23~25°C

(migrate)

Each of the carrier-attached copper foils (squares of 550 mm × 550 mm) before the formation of the resin layer was attached to the lanthanide resin, and then the carrier foil was peeled off. The thickness of the exposed ultra-thin copper layer was 1.5 μm by soft etching. Thereafter, after washing and drying, DF (manufactured by Hitachi Chemical Co., Ltd., trade name: RY-3625) was laminated on the ultra-thin copper layer. The exposure was carried out under the conditions of 15 mJ/cm ² , and a liquid jet oscillation was performed for 1 minute using a developing solution (sodium carbonate) at 38 ° C to form a photoresist pattern with a line and a gap (L/S) = 15 μm / 15 μm. Then, after plating with copper sulfate (CUBRITE 21 manufactured by Ebara-Udylite) at a height of 15 μm, the DF was peeled off with a stripping solution (sodium hydroxide). Thereafter, the ultra-thin copper layer was etched away with a sulfuric acid-hydrogen peroxide-based etchant to form a wiring of L/S = 15 μm / 15 μm. 100 wiring boards were cut out from the obtained wiring substrate in accordance with each of the above-mentioned areas of 55 mm × 55 mm.

Each of the obtained wiring substrates was evaluated for the presence or absence of insulation deterioration between wiring patterns under the following measurement conditions using a migration measuring machine (MIG-9000 manufactured by IMV). About 100 wiring bases The plate was evaluated for the number of substrates on which migration occurred.

Further, in the second embodiment, the above-described migration was carried out by forming a wiring having a line-to-gap distance of 20 μm (L/S = 8 μm / 12 μm, L/S = 10 μm / 10 μm, L / S = 12 μm / 8 μm). Evaluation. Further, in the third embodiment, the distance between the line and the gap is 20 μm (L/S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm), and the distance between the lines and the gap is 15 μm. The above migration was evaluated by wiring (L/S = 5 μm/10 μm, L/S = 8 μm / 7 μm). Further, when the distance between the line and the gap is 15 μm, the thickness of the plating is set to 10 μm. As a result, when the wiring of L/S=8 μm/12 μm, L/S=10 μm/10 μm, and L/S=12 μm/8 μm was formed using the copper foil with a carrier of Example 2, the in-plane migration generation rates were respectively 2/100, 2/100, 3/100. Further, L/S = 8 μm / 12 μm, L / S = 10 μm / 10 μm, L / S = 12 μm / 8 μm, L / S = 5 μm / 10 μm, L / S = 8 μm were formed using the carrier copper foil of Example 3. In the case of /7 μm wiring, the in-plane migration generation rates were 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

<Measurement conditions>

Threshold: initial resistance drop of 60%

Measurement time: 1000h

Voltage: 60V

Temperature: 85 ° C

Relative humidity: 85% RH

(peel strength)

The peeling strength of the ultra-thin copper layer from the resin substrate was measured for the copper foil with a carrier which was produced with the resin layer (in which the resin layer was not formed). A BT substrate (Bismaleimide. Sanshi Resin, GHPL-830MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as a resin substrate, which was laminated on the resin layer side of the carrier-attached copper foil at Mitsubishi Gas Chemical A copper clad laminate is produced by heating and pressure bonding under the recommended conditions of the company. Thereafter, after the carrier was peeled off, a circuit having a width of 10 mm was formed by wet etching, and 10 measurement samples were prepared in each of the examples and the comparative examples. Thereafter, the extremely thin copper layer forming the circuit was peeled off, and the 90-degree peel strength was measured for 10 samples, and the average value, the maximum value, the minimum value, and the peel strength unevenness ((maximum-minimum value) of the peel strength were determined. / average × 100 (%)). The BT substrate is a representative substrate for a semiconductor package substrate. The peel strength from the extremely thin copper layer of the BT substrate when the BT substrate is laminated is preferably 0.70 kN/m or more, more preferably 0.85 kN/m or more.

Claims (33)

A copper foil with carrier, which is provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Rz of the surface of the ultra-thin copper layer is measured by a contact roughness meter according to JIS B0601- In 1982, the measurement was 1.5 μm or less, and the standard deviation of Rz was 0.1 μm or less. The carrier copper foil of claim 1, wherein the ultra-thin copper layer is roughened. The carrier copper foil according to claim 1 or 2, wherein an average value of Rt of the surface of the ultra-thin copper layer is 2.0 μm or less by a contact type roughness meter according to JIS B0601-2001, and the standard of Rt The deviation is 0.1 μm or less. The carrier-attached copper foil according to claim 1 or 2, wherein the average value of Ra of the surface of the ultra-thin copper layer is 0.2 μm or less by the contact type roughness meter according to JIS B0601-1982, and the standard of Ra The deviation is 0.03 μm or less. The carrier copper foil according to claim 1 or 2, wherein an average value of Rz of the surface of the ultra-thin copper layer is 1.0 μm or less. The carrier copper foil according to item 5 of the patent application, wherein an average value of Rz of the surface of the ultra-thin copper layer is 0.5 μm or less. A copper foil with carrier, which is provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Rt of the surface of the ultra-thin copper layer is measured by a contact roughness meter according to JIS B0601- The measurement was performed in 2001 and was 2.0 μm or less, and the standard deviation of Rt was 0.1 μm or less. The copper foil with a carrier of the seventh aspect of the patent application, wherein the ultra-thin copper layer is roughened. The carrier copper foil according to claim 7 or 8, wherein the average value of Rz of the surface of the ultra-thin copper layer is 1.5 μm by using a contact type roughness meter according to JIS B0601-1982. Hereinafter, the standard deviation of Rz is 0.1 μm or less. The carrier-attached copper foil according to claim 7 or 8, wherein the average value of Ra of the surface of the ultra-thin copper layer is 0.2 μm or less by the contact type roughness meter according to JIS B0601-1982, and the standard of Ra is The deviation is 0.03 μm or less. The carrier copper foil according to claim 7 or 8, wherein the average Rt of the surface of the ultra-thin copper layer is 1.0 μm or less. A copper foil with carrier, which is provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Ra of the surface of the ultra-thin copper layer is measured by a contact roughness meter according to JIS B0601- In 1982, the measurement was carried out to be 0.2 μm or less, and the standard deviation of Ra was 0.03 μm or less. The carrier copper foil of claim 12, wherein the ultra-thin copper layer is roughened. The carrier copper foil according to claim 12 or 13, wherein the average value of Rz of the surface of the ultra-thin copper layer is 1.5 μm or less by the contact type roughness meter according to JIS B0601-1982, and the standard of Rz The deviation is 0.1 μm or less. The carrier copper foil according to claim 12 or 13, wherein the average value of Rt of the surface of the ultra-thin copper layer is 2.0 μm or less by the contact type roughness meter according to JIS B0601-2001, and the standard of Rt The deviation is 0.1 μm or less. The carrier copper foil according to claim 12 or 13, wherein the average value of Ra of the surface of the ultra-thin copper layer is 0.15 μm or less. A printed wiring board produced by using the carrier copper foil of any one of claims 1 to 16. The printed wiring board of claim 17, comprising: an insulating substrate; and a copper circuit provided on the insulating substrate; The circuit width of the above copper circuit is less than 20 μm, and the gap width between adjacent copper circuits is less than 20 μm. The printed wiring board of claim 17, comprising: an insulating substrate; and a copper circuit provided on the insulating substrate, wherein the copper circuit has a circuit width of 17 μm or less, and a gap width between the adjacent copper circuits is 17 μm or less. . For example, in the printed wiring board of claim 17, wherein the distance between the line and the gap is less than 40 μm. For example, in the printed wiring board of claim 17, wherein the distance between the line and the gap is 34 μm or less. A printed circuit board produced by using the carrier copper foil of any one of claims 1 to 16. The printed circuit board of claim 22, comprising: an insulating substrate; and a copper circuit disposed on the insulating substrate, wherein a circuit width of the copper circuit is less than 20 μm, and a gap width between adjacent copper circuits is less than 20 μm . The printed circuit board of claim 22, comprising: an insulating substrate; and a copper circuit provided on the insulating substrate, wherein the copper circuit has a circuit width of 17 μm or less, and a gap width between adjacent copper circuits is 17 μm or less. . For example, in the printed circuit board of claim 22, the distance between the line and the gap is less than 40 μm. For example, in the printed circuit board of claim 22, wherein the distance between the line and the gap is 34 μm or less. A copper-clad laminate produced by using the carrier-attached copper foil according to any one of claims 1 to 16. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 16; and stacking the copper foil with the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then, by semi-additive method, subtractive method, partial addition method Or the step of forming a circuit by any of the modified semi-additive methods. A method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of any one of claims 1 to 16; and burying the circuit a step of forming a resin layer on the surface of the ultra-thin copper layer of the copper foil with a carrier; a step of forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier; and by peeling off the carrier The ultra-thin copper layer is removed, and the circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed. The method for producing a printed wiring board according to claim 29, wherein the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and to use the bonding. The step of forming the above circuit is performed on the copper foil with a carrier of the above resin layer. A method of manufacturing a printed wiring board according to claim 30, wherein the method is as described above Another carrier-attached copper foil on the resin layer is the carrier-attached copper foil of any one of claims 1 to 16. The method of manufacturing a printed wiring board according to any one of claims 29 to 31, wherein the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified half. Any one of the methods of addition is carried out. The method for producing a printed wiring board according to any one of claims 29 to 31, further comprising the step of forming a substrate on a carrier side surface of the carrier copper foil before peeling off the carrier.